Silane-terminated polyurethanes with high strength and high elongation

ABSTRACT

A silane-terminated polyurethane composition is the reaction product of a silane-terminated polyurethane prepolymer component, a silane-terminated monomeric diisocyanate, and optionally at least one multifunctional trisilane or tetrasilane component. A method for making a composition includes (a) providing a silane-terminated polyurethane prepolymer component, a silane-terminated monomeric diisocyanate component, and optionally at least one multifunctional trisilane or tetrasilane component, and (b) combining the prepolymer component, monomeric component, and optional multifunctional silane component to form a silane-terminated polyurethane reaction product with a tensile strength of about 4 MPa or greater and an elongation of about 200% or greater.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 10/808,084 filed onMar. 24, 2004, now U.S. Pat. No. 7,482,420.

BACKGROUND

Polyurethane materials demonstrate a unique combination of performanceproperties, including excellent abrasion resistance, flexibility,hardness, chemical resistance, solvent resistance, light stability, andweatherability.

The performance properties of polyurethanes make them suitable for manyuseful products, including coatings, adhesives, sealants, andcompositions. Standard polyurethanes, however, have disadvantagesrelated to the presence of isocyanates, such as sensitivity to humidapplication conditions. Silane-terminated polyurethanes can beformulated to be isocyanate-free, but have not previously demonstratedthe high tensile strength and high elongation properties required forhigh performance applications.

What is needed in the art are polyurethane materials that are notsensitive to humid application conditions. What is also needed in theart is a high performance silane-terminated polyurethane that isisocyanate-free and has both high strength and high elongation. Theseproperties are met with the reaction product of a silane-terminatedpolyurethane prepolymer and a silane-terminated monomeric diisocyanate.

SUMMARY

A silane-terminated polyurethane composition is provided, comprising thereaction product of a silane-terminated polyurethane prepolymercomponent, a silane-terminated monomeric diisocyanate component, andoptionally a trisilane or tetrasilane component.

In certain embodiments of the silane-terminated polyurethanecomposition:

-   -   a) the silane-terminated polyurethane prepolymer component        comprises at least one of:        -   i) a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 1.1:1 to about            2:1, said prepolymer reaction product terminated with an            aminosilane endcapper of the formula:            R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   or a mercaptosilane endcapper of the formula:            HS—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   wherein R represents a C₁ to C₁₀ alkyl group, a group having            the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the            formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀            linear, branched or cyclic alkylene group; R¹ represents a            CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³            represents a C₁ to C₁₃ alkyl group; R⁴ represents a C₁ to            C₁₃ alkyl group; and x is 0 or 1; or        -   ii) a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 0.5:1 to about            0.9:1, said prepolymer reaction product terminated with an            isocyanatosilane endcapper of the formula:            OCN—A²—Si(R¹)_(x)(OR²)_(3-x)        -   wherein A² represents a C₁ to C₆ linear or branched alkylene            group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁            to C₄ alkyl group; and x is 0 or 1;    -   b) the silane-terminated monomeric diisocyanate component        comprises at least one monomeric diisocyanate fully reacted with        an aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1; and    -   c) the optional trisilane or tetrasilane component comprises at        least one of a polyether trisilane component, a polyether        tetrasilane component, or a low molecular weight silane adduct        comprising at least one of a trisilane adduct or a tetrasilane        adduct.

A multicomponent formulation is provided comprising:

-   -   a) at least one of:        -   i) a silane-terminated polyurethane prepolymer component            comprising a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 1.1:1 to about            2:1, said prepolymer reaction product terminated with an            aminosilane endcapper of the formula:            R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   or a mercaptosilane endcapper of the formula:            HS—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   wherein R represents a C₁ to C₁₀ alkyl group, a group having            the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the            formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀            linear, branched or cyclic alkylene group; R¹ represents a            CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³            represents a C₁ to C₁₃ alkyl group; R⁴ represents a C₁ to            C₁₃ alkyl group; and x is 0 or 1; or        -   ii) a silane-terminated polyurethane prepolymer component            comprising a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 0.5:1 to about            0.9:1, said prepolymer reaction product terminated with an            isocyanatosilane endcapper of the formula:            OCN—A²—Si(R¹)_(x)(OR²)_(3-x)        -   wherein A² represents a C₁ to C₆ linear or branched alkylene            group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁            to C₄ alkyl group; and x is 0 or 1;    -   b) at least one monomeric diisocyanate fully reacted with an        aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1; and    -   c) optionally at least one of a polyether trisilane component, a        polyether tetrasilane component, or a low molecular weight        silane adduct comprising at least one of a trisilane adduct or a        tetrasilane adduct;        wherein when components a, b, and optionally c are combined, a        silane-terminated polyurethane reaction product is formed that        has a tensile strength of about 4 MPa or greater and an        elongation of about 200% or greater.

A method for making a silane-terminated polyurethane composition isprovided comprising:

-   -   a) providing a prepolymer component, a monomeric component, and        optionally at least one multifunctional component, wherein the        prepolymer component comprises a silane-terminated polyurethane        prepolymer, the monomeric component comprises a        silane-terminated monomeric diisocyanate, and the optional        multifunctional component comprises at least one of a trisilane        or tetrasilane component; and    -   b) combining the prepolymer component, the monomeric component,        and optionally the at least one multifunctional component to        form a silane-terminated polyurethane reaction product;        wherein the silane-terminated polyurethane reaction product has        a tensile strength of about 4 MPa or greater and an elongation        of about 200% or greater.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a three dimensional representation of tensile strength ofcertain silane-terminated polyurethane reaction products synthesizedfrom isocyanate terminated prepolymers of disocyanate and polyol havinga ratio of isocyanate groups to hydroxy groups less than 2:1, blendedwith monomeric disocyanates to increase the ratio above 2:1.

FIG. 2 is a three dimensional representation of elongation percentage ofcertain silane-terminated polyurethane reaction products synthesizedfrom isocyanate terminated prepolymers of disocyanate and polyol havinga ratio of isocyanate groups to hydroxy groups less than 2:1, blendedwith monomeric disocyanates to increase the ratio above 2:1.

FIG. 3 is a graph showing the tensile strength and elongation percentagefor a silane-terminated polyurethane reaction product according tocertain embodiments as a function of the weight percentage of polyethertrisilane component.

FIG. 4 is a graph showing the tensile strength and elongation percentagefor a silane-terminated polyurethane reaction product according tocertain embodiments as a function of the weight percentage of lowmolecular weight trisilane component.

DETAILED DESCRIPTION

A silane-terminated polyurethane composition comprises the reactionproduct of a silane-terminated polyurethane prepolymer component, asilane-terminated monomeric diisocyanate component, and optionally atrisilane or tetrasilane component.

The silane-terminated polyurethane composition may also comprise thereaction product of a silane-terminated polyurethane prepolymercomponent, at least one monomeric diisocyanate fully reacted with anaminosilane endcapper or a mercaptosilane endcapper, and optionally atleast one multifunctional component selected from the group consistingof a polyether trisilane component, a polyether tetrasilane component,or a low molecular weight silane adduct comprising at least one of atrisilane adduct or a tetrasilane adduct.

In certain embodiments, the silane-terminated polyurethane prepolymercomponent comprises a prepolymer reaction product of at least onediisocyanate and at least one polyol with a mole ratio of isocyanategroups to hydroxy groups of about 1.1:1 to about 2:1, wherein theprepolymer reaction product is terminated with an aminosilane endcapperof the formula: R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or a mercaptosilaneendcapper of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x), wherein Rrepresents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

In other embodiments, the silane-terminated polyurethane prepolymercomponent comprises a prepolymer reaction product of at least onediisocyanate and at least one polyol with a mole ratio of isocyanategroups to hydroxy groups of about 0.5:1 to about 0.9:1, wherein theprepolymer reaction product is terminated with an isocyanatosilaneendcapper of the formula: OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A²represents a C₁ to C₆ linear or branched alkylene group; R¹ represents aCH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; and x is 0or 1. The silane-terminated polyurethane prepolymer component may alsocomprise the above prepolymer reaction products terminated with acombination of aminosilane, mercaptosilane, and isocyanatosilaneendcappers.

Generally, isocyanatosilanes are used to endcap hydroxyterminatedprepolymers (i.e., having a mole ratio of isocyanate groups to hydroxygroups (NCO/OH ratios) less than 1.0), and aminosilanes ormercaptosilanes are used to endcap NCO-terminated prepolymers (i.e.,NCO/OH ratios greater than 1.0) and the diisocyanates.

The silane-terminated polyurethane composition may further comprise thereaction product of the silane-terminated polyurethane prepolymercomponent and at least one monomeric diisocyanate fully reacted with anaminosilane endcapper of the formula: R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), ora mercaptosilane endcapper of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x),wherein R represents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

In certain embodiments, the silane-terminated polyurethane compositioncomprises the reaction product of about 70 to about 95 percent by weightsilane-terminated polyurethane prepolymer and about 5 to about 30percent by weight silane-terminated monomeric diisocyanate, optionallyincluding up to about 30 percent by weight trisilane or tetrasilanecomponent, discussed in more detail below.

The performance capabilities of the composition can be expressed interms of measured physical properties such as tensile strength andelongation percentage measured by a standard test method such as ASTM D412. Tensile strength is the force needed to stretch a material until itbreaks. Elongation percentage or elongation at break is how much thematerial stretches before it breaks, as a percentage of its originaldimensions.

The polyol of the silane-terminated polyurethane prepolymer componentmay comprise a diol or higher functionality polyol, and may be selectedfrom the group consisting of polyether polyols, polyester polyols, andcombinations thereof.

For illustration purposes but not by way of limitation, the polyol maybe selected from the group consisting of polypropylene glycols,polytetramethylene glycols, polyoxyalkylene diols and triols,polycaprolactone diols and triols, and combinations thereof.

Polyoxyalkylene polyols include polyethers prepared by thecopolymerization of cyclic ethers selected from the group consisting ofethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran,and mixtures of these cyclic ethers, with aliphatic polyols selectedfrom the group consisting of ethylene glycol, 1,3-butanediol, diethyleneglycol, dipropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butylene glycol, and mixtures of these aliphatic polyols.Representative polyoxyalkylene polyols include the described polyethers,polyethylene glycols, polypropylene glycols, polytetramethylene glycols,and mixtures thereof.

Representative examples of polyols include Voranol™ 220-028 and Voranol™220-056N (available from Dow Chemical Company, Midland, Mich.) as wellas Acclaim™ 4200, Acclaim™ 6300, Acclaim™ 8200 and Acclaim™ 12200(available from Bayer Corporation, Pittsburgh, Pa.).

In certain embodiments, the polyol of the silane-terminated polyurethaneprepolymer component has a molecular weight in the range of about 500 toabout 20000. In other embodiments, the polyol has a molecular weight inthe range of about 4000 to about 12000. In another embodiment, thepolyol comprises a polypropylene glycol with a number average molecularweight in the range of about 4000 to about 12000, and the polypropyleneglycol has a degree of unsaturation of less than about 0.04 meq/g. Themolecular weight is either a calculated molecular weight, i.e. the sumof the atomic weights of the atoms making up the material, or themolecular weight is a number average molecular weight determined basedon end group analysis or measurement of colligative properties byebulliometry, cryoscopy, or membrane osmometry.

For illustration purposes but not by way of limitation, eachdiisocyanate reactant may be selected from the group consisting ofhexamethylene diisocyanate (HDI), 4,4′-diphenylmethane diisocyanate(MDI), 2,4′-diphenylmethane diisocyanate, blends of 4,4′-diphenylmethanediisocyanate (MDI) with 2,4′-diphenylmethane diisocyanate, 2,4-toluenediisocyanate (TDI), 2,6-toluene diisocyanate, blends of 2,4-toluenediisocyanate (TDI) with 2,6-toluene diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof. In oneembodiment, the diisocyanate comprises a blend of 4,4′-diphenylmethanediisocyanate (MDI) with 2,4′-diphenylmethane diisocyanate (such asMondur ML diisocyanate available from Bayer Corporation, Pittsburgh,Pa.).

The aminosilane endcapper for polyurethane prepolymers and monomericdiisocyanates may be selected from the group consisting of secondaryaminosilanes having two methoxy groups, secondary aminosilanes havingthree methoxy groups, secondary aminosilanes having two ethoxy groups,secondary aminosilanes having three ethoxy groups, and combinationsthereof. In certain embodiments, the aminosilane endcapper is selectedfrom the group consisting of bis(trimethoxysilylpropyl)amine,3-ethylamino-2-methylpropyltrimethoxysilane,N-(n-butyl)-3-aminopropyltrimethoxysilane, and combinations thereof.

A mercaptosilane endcapper for polyurethane prepolymers and monomericdiisocyanates may include, but need not be limited to,(3-mercaptopropyl)trimethoxysilane.

The isocyanatosilane endcapper for polyurethane prepolymers may beselected from the group consisting of isocyanatosilanes having twomethoxy groups, isocyanatosilanes having three methoxy groups,isocyanatosilanes having two ethoxy groups, isocyanatosilanes havingthree ethoxy groups, and combinations thereof. In one embodiment, theisocyanatosilane endcapper comprises3-isocyanatopropyl-trimethoxysilane.

In certain embodiments, the polyether trisilane component may comprisethe reaction product of at least one polyether triol terminated with anisocyanatosilane endcapper of the formula: OCN—A²—Si(R¹)_(x)(OR²)_(3-x)wherein A² represents a C₁ to C₆ linear or branched alkylene group; R¹represents a CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group;and x is 0 or 1. In other embodiments, the polyether trisilane componentmay comprise the multifunctional reaction product of at least onepolyether triol terminated with at least one diisocyanate with a moleratio of isocyanate groups to hydroxy groups of about 1.5:1 to about2:1, wherein the multifunctional reaction product is terminated with anaminosilane endcapper of the formula: R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), ora mercaptosilane endcapper of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x),wherein R represents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

A representative reaction of a polyether triol with an isocyanatoendcapper to form a polyether trisilane is shown in Formula 1.

The polyether tetrasilane component may comprise the reaction product ofat least one polyether tetraol terminated with an isocyanatosilaneendcapper of the formula: OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A²represents a C₁ to C₆ linear or branched alkylene group; R¹ represents aCH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; and x is 0or 1. In certain embodiments, the polyether tetrasilane component maycomprise the multifunctional reaction product of at least one polyethertetraol terminated with at least one diisocyanate with a mole ratio ofisocyanate groups to hydroxy groups of about 1.5:1 to about 2:1, whereinthe multifunctional reaction product is terminated with an aminosilaneendcapper of the formula: R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or amercaptosilane endcapper of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x),wherein R represents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

The low molecular weight silane adduct may comprise the reaction productof at least one of the following sets of reactants:

-   -   a) i) at least one of HS—A¹—Si(R¹)_(x)(OR²)_(3-x), or        R⁷—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), and        -   ii) at least one of:

-   -   b) R⁵—(—OH)_(y) and OCN—A²—Si(R¹)_(x)(OR²)_(3-x);    -   c) i) at least one of:        -   R⁵—(—NHR⁷)_(y), or        -   [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and        -   ii) at least one of:

-   -   d) i) [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and        -   ii) a diisocyanate;    -   e) i) a polyether triamine and ii) at least one of

-   -   f) at least one of:        -   i) diethylenetriamine or triethylenetetramine, and ii) at            least one of:

wherein A² represents a C₁ to C₆ linear, or branched alkylene group; A³represents a C₁ to C₁₀ linear, branched or cyclic alkylene groupoptionally interrupted with one or more ether oxygen atoms; R⁵represents a branched aliphatic hydrocarbon residue, a branchedaliphatic ether residue, or an alkyl-substituted isocyanurate residue;R⁶ represents H or a CH₃ group; R⁷ represents H, a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; x is 0 or 1; and yis 3 or 4.

Examples of R⁵ containing molecules include, but are not limited to, thestructures set forth below.

Representative reactions for the synthesis of low molecular weighttrisilanes are shown in Formula 2.

In certain embodiments, the silane-terminated polyurethane compositioncomprises the reaction product of about 40 to about 98 percent by weightsilane-terminated polyurethane prepolymer, about 2 to about 40 percentby weight silane-terminated monomeric diisocyanate, and optionally up toabout 30 percent by weight trisilane or tetrasilane component. In otherembodiments, the silane-terminated polyurethane composition comprisesthe reaction product of about 65 to about 85 percent by weightsilane-terminated polyurethane prepolymer, about 10 to about 25 percentby weight silane-terminated monomeric diisocyanate, and optionally up toabout 10 percent by weight trisilane or tetrasilane component. Thesilane-terminated polyurethane compositions exhibit high tensilestrengths and high elongation values, and are suitable for highperformance applications.

Polyurethane compositions may be supplied to the trade as multicomponent(i.e., separately packaged) formulations. Accordingly, a multicomponentformulation may comprise:

-   -   (a) at least one of:        -   (i) a silane-terminated polyurethane prepolymer component            comprising a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 1.1:1 to about            2:1, said prepolymer reaction product terminated with an            aminosilane endcapper of the formula:            R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or a mercaptosilane endcapper            of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x), wherein R            represents a C₁ to C₁₀ alkyl group, a group having the            formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the            formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀            linear, branched or cyclic alkylene group; R¹ represents a            CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³            represents a C₁ to C₁₃ alkyl group; R⁴ represents a C₁ to            C₁₃ alkyl group; and x is 0 or 1; or        -   (ii) a silane-terminated polyurethane prepolymer component            comprising a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 0.5:1 to about            0.9:1, said prepolymer reaction product terminated with an            isocyanatosilane endcapper of the formula:            OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A² represents a C₁ to            C₆ linear or branched alkylene group; R¹ represents a CH₃ or            C₂H₅ group; R² represents a C₁ to C₄ alkyl group; and x is 0            or 1;    -   (b) at least one monomeric diisocyanate fully reacted with an        aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or a mercaptosilane endcapper of        the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x), wherein R represents a        C₁ to C₁₀ alkyl group, a group having the formula        —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CHI(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1; and    -   (c) optionally at least one of a polyether trisilane component,        a polyether tetrasilane component, or a low molecular weight        silane adduct comprising at least one of a trisilane adduct or a        tetrasilane adduct;        wherein when components a, b, and optionally c are combined, a        silane-terminated polyurethane reaction product is formed that        has a tensile strength of about 4 MPa or greater and an        elongation of about 200% or greater.

In certain embodiments, a silane-terminated polyurethane reactionproduct is formed that has a tensile strength of about 4 MPa or greater.In other embodiments, the silane-terminated polyurethane reactionproduct has a tensile strength of about 8 MPa or greater. In yet otherembodiments, the silane-terminated polyurethane reaction product has atensile strength of about 10 MPa or greater.

In some embodiments, the silane-terminated polyurethane reaction producthas an elongation at break of about 200% or greater. In otherembodiments, the silane-terminated polyurethane reaction product has anelongation of about 250% or greater. In certain other embodiments, thesilane-terminated polyurethane reaction product has an elongation ofabout 300% or greater.

The silane-terminated polyurethane reaction product exhibits acombination of high tensile strength and high elongation and istherefore suitable for high performance applications such as coatings,sealants, adhesives, and sports track binders.

Component polyols, diisocyanates, and silanes of the multicomponentformulations are selected from the same groups as described above withrespect to the other embodiments. The silane-terminated polyurethanereaction products formed from the multicomponent formulations aresuitable for use as coatings, sealants, adhesives, sports track bindersand other high performance applications.

The described multicomponent formulations, silane-terminatedpolyurethane compositions, and silane-terminated polyurethane reactionproducts may comprise additional optional components which may include,but are not limited to, UV absorbers, antioxidants, stabilizers,mildewcides, biocides, fungicides, fire and flame retardants, fillers,pigments, plasticizers, solvents, catalysts, adhesion promoters, flowand leveling additives, wetting agents, antifoaming agents, rheologymodifiers, and mixtures thereof. By way of example, but limitation, thereaction products may optionally contain up to about 5 percent by weightof UV absorbers, up to about 5 percent by weight of antioxidants, up toabout 5 percent by weight of stabilizers, up to about 2 percent byweight of mildewcides, up to about 2 percent by weight of biocides, upto about 2 percent by weight of fungicides, up to about 20 percent byweight of fire or flame retardants, up to about 80 percent by weight offillers, up to about 10 percent by weight of pigments, up to about 30percent by weight of plasticizers, up to about 30 percent by weight ofsolvents, up to about 5 percent by weight of catalysts, up to about 5percent by weight of adhesion promoters, up to about 10 percent byweight of flow and leveling additives, up to about 5 percent by weightof wetting agents, up to about 2 percent by weight of antifoamingagents, and/or up to about 20 percent by weight of rheology modifiers.

Suitable UV absorbers, stabilizers, antioxidants, mildewcides, biocides,and fungicides are materials known to those skilled in the art, andprotect the multicomponent formulations, silane-terminated polyurethanecompositions, and silane-terminated polyurethane reaction products fromharmful effects of weathering and biological agents.

Suitable UV stabilizers may comprise 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, esters of substituted and unsubstituted benzoicacids, acrylates, nickel compounds, sterically hindered amines,oxanilides, 2-(2-hydroxyphenyl)-1,3,5-triazines, and mixtures thereof.

Representative examples of suitable UV stabilizers are set forth in U.S.patent application Ser. No. 10/797,548, filed Mar. 10, 2004, which isincorporated herein by reference.

Suitable antioxidants may comprise alkylated monophenols,alkylthiomethylphenols, hydroquinones and alkylated hydroquinones,tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-,N- and S-benzyl compounds, hydroxybenzylated malonates, aromatichydroxybenzyl compounds, triazine compounds, benzylphosphonates,acylaminophenols, esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydricalcohols, esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols, esters ofbeta-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenyl aceticacid with mono- or polyhydric alcohols, amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ascorbic acidand derivatives, aminic antioxidants, and mixtures thereof.

Representative examples of suitable antioxidants are set forth in U.S.patent application Ser. No. 10/797,548, filed Mar. 10, 2004, which isincorporated herein by reference.

Suitable fungicides, mildewcides, and biocides may comprise4,4-dimethyloxazolidine, 3,4,4-trimethyloxazolidine, modified bariummetaborate, potassium N-hydroxy-methyl-N-methyldithiocarbamate,2-(thiocyanomethylthio) benzothiazole, potassium dimethyldithiocarbamate, adamantane, N-(trichloromethylthio) phthalimide,2,4,5,6-tetrachloroisophthalonitrile, orthophenyl phenol,2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copperoctoate, organic arsenic, tributyl tin oxide, zinc naphthenate, copper8-quinolinate, and mixtures thereof.

The fire retardants may comprise any material that provides selfextinguishing properties. Suitable examples of the fire retardantinclude, but are not limited to, phosphates such as monoammoniumphosphate, ammonium polyphosphate, melamine and melamine derivativessuch as melamine phosphate, melamine cyanurate and melaminepolyphosphate, triphenyl phosphate, tricresyl phosphate, tributylphosphate, tri(2-chloroethyl)phosphate, dimethyl methyl phosphonate,zinc borate, expandable graphite, exfoliated graphite, acid treatednatural graphite flakes, antimony/halogen systems and mixtures thereof.The fire retardant can be a liquid or a solid. A solid fire retardantmay be ground to a micron size, typically referred to as micronized.Additionally, the fire retardant may include but is not limited to selfextinguishing agents and flame retardants. In some embodiments, the fireretardant is ammonium polyphosphate. In other embodiments, an aluminumoxide smoke retardant is used in combination with the ammoniumpolyphosphate.

The multicomponent formulations, silane-terminated polyurethanecompositions, and silane-terminated polyurethane reaction products mayalso comprise at least one filler, for example a solid inert to othermaterials in the compositions and reaction products. Resilient particlesare useful fillers. Suitable examples of the filler include fibers,rubber particles, and cork particles. Other suitable examples of fillersinclude, but are not limited to carbon black, titanium dioxide, glass,such as crushed glass or glass spheres, metal such as iron particles,quartz, silica such as amorphous precipitated silica, hydrophilic fumedsilicas, hydrophobic fumed silicas, kaolin, mica, diatomaceous earth,talc, zeolites, clays, aluminum hydroxide, sulfates such as aluminumsulfate, barium sulfate, and calcium sulfate, calcium carbonate,dolomite, organic and inorganic fibers, barytes, limestone,wollastonite, perlite, flint powder, kryolite, alumina, aluminatrihydrate, polymer granules and powders such as granulated ormicronized polyethylene and granulated or micronized polypropylene,melamine, fibers such as polypropylene or nylon, zinc oxide, andmixtures thereof. Carbon black and titanium dioxide may be used as botha filler and a pigment.

The multicomponent formulations, silane-terminated polyurethanecompositions, and silane-terminated polyurethane reaction products mayalso comprise a coloring agent, such as a pigment or a dye, to provide adesired color to the sealant. Examples of coloring agents are carbonblack and titanium dioxide which may be in the rutile form, but othercoloring agents are also useful. Carbon black and titanium dioxide mayact as both pigments and fillers in the sealant. Additional examples ofpigments include, but are not limited to, barium sulfate, zinc oxide,zinc sulfide, basic lead carbonate, antimony trioxide, lithopones (zincsulfide and barium sulfate), inorganic color pigments such as ironoxides, carbon black, graphite, luminescent pigments, zinc yellow, zincgreen, ultramarine, manganese black, antimony black, manganese violet,Paris blue, and Schweinfurter green, organic color pigments such assepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow,indigo, azo dyes, anthraquinonoid and indigoid dyes, as well asdioxazine, quinacridone, phthalocyanine, isoindolinone, and metalcomplex pigments, and mixtures thereof.

Suitable examples of plasticizers include, but are not limited to,phthalic acid esters such as dioctyl phthalate, di-isononyl phthalate,di-isodecyl phthalate, butyl benzyl phthalate, and di-isobutylphthalate, adipic acid esters such as dioctyl adipate and diisononyladipate, sulfonic acid esters, and mixtures thereof.

Suitable examples of solvents include, but are not limited to, aliphatichydrocarbons such as mineral spirits, aromatic hydrocarbons such astoluene, xylene, solvent naphtha, and Aromatic 100, esters such as ethylacetate, butyl acetate, and propylene glycol diacetate, ethers such asdipropylene glycol dimethyl ether, ketones such as methyl ethyl ketone,methyl isobutyl ketone, and cyclohexanone, and mixtures thereof.

Suitable examples of catalysts include, but are not limited to,dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, stannousoctoate/laurylamine, dibutyltin bis(acetylacetonate), dibutyltindichloride, dibutyltin bis(2-ethylhexyl mercaptoacetate), monobutyltintris(2-ethylhexyl mercaptoacetate), butyltin trichloride, andcombinations thereof.

The multicomponent formulations, polyurethane compositions, andpolyurethane reaction products may additionally comprise surfaceadditives such as flow and leveling additives, wetting agents, andantifoaming agents to facilitate application of the material. Examplesof flow and leveling additives, wetting agents, and antifoaming agentsinclude silicones, modified silicones, polyacrylates, and hydrocarbonssuch as petroleum components and mixtures. Examples of suitable flowadditives include, but are not limited to, polyester modified acrylicfunctional poly-di-methyl siloxanes such as BYK®-371, and polyacrylatecopolymers such as BYK®-358, (both available from BYK-Chemie USA,Wallingford, Conn.), and fluorosurfactants such as 3M™ Fluorad™ FC-4430Fluorosurfactant (available from 3M Company, St. Paul, Minn.).

The multicomponent formulations, polyurethane compositions, andpolyurethane reaction products may additionally comprise an adhesionpromoter. Examples of adhesion promoters include, but are not limited to3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,1[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea,[3-(2-aminoethylamino)propyl]trimethoxysilane,[3-(2-aminoethylamino)propyl]triethoxysilane,3-glycidyloxypropyl-trimethoxysilane,3-glycidyloxypropyl-triethoxysilane,2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane,2-(3,4-epoxycyclohexyl)ethyl-triethoxysilane,3-(phenylamino)propyl-trimethoxysilane,3-(phenylamino)propyl-triethoxysilane,bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine,3-aminopropyl-methyldimethoxysilane, 3-aminopropyl-methyldiethoxysilane,3-mercaptopropyl-methyldimethoxysilane,3-mercaptopropyl-methyldiethoxysilane,[3-(2-aminoethylamino)propyl]methyldimethoxysilane,[3-(2-aminoethylamino)propyl]methyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl-methyldiethoxysilane, andcombinations thereof.

The multicomponent formulations, silane-terminated polyurethanecompositions, and silane-terminated polyurethane reaction products mayalso comprise a rheology modifier to increase the viscosity of thematerial immediately after application to a substrate. This can preventthe reaction products from dripping or running when initially applied toa substrate. Suitable examples of the rheology modifier include, but arenot limited to, polyureas, fumed silica, hydroxyethyl cellulose,hydroxypropyl cellulose, polyamide waxes, modified castor oil, and clayintercalated with organic cations.

The additional components may be incorporated separately or may becombined with any reaction component.

In certain embodiments, the described multicomponent formulations,silane-terminated polyurethane compositions, and silane-terminatedpolyurethane reaction products may comprise binders that can bind andhold together fillers, aggregates, and other components in a polymermatrix. In other embodiments, the binders may also comprise coatings,sealants, adhesives, or other polymer matrices without any addedfillers, aggregates, or other components.

The silane-terminated polyurethane composition may be made by a methodcomprising:

(a) providing a prepolymer component, a monomeric component, andoptionally at least one multifunctional component, wherein theprepolymer component comprises a silane-terminated polyurethaneprepolymer, the monomeric component comprises a silane-terminatedmonomeric diisocyanate, and the optional multifunctional componentcomprises at least one of a trisilane or tetrasilane component; and

(b) combining the prepolymer component, the monomeric component, andoptionally the at least one multifunctional component to form asilane-terminated polyurethane reaction product, wherein the reactionproduct has a tensile strength of about 4 MPa or greater and anelongation of about 200% or greater.

In certain embodiments, the silane-terminated reaction product has atensile strength of about 4 MPa or greater. In other embodiments, thesilane-terminated reaction product has a tensile strength of about 8 MPaor greater. In yet other embodiments, the silane-terminated reactionproduct has a tensile strength of about 10 MPa or greater. In someembodiments, the silane-terminated reaction product has an elongation atbreak of about 200% or greater. In other embodiments, thesilane-terminated reaction product has an elongation of about 250% orgreater. In certain other embodiments, the silane-terminated reactionproduct has an elongation of about 300% or greater.

In some embodiments, the silane-terminated polyurethane prepolymercomponent comprises an endcapped prepolymer reaction product of at leastone diisocyanate and at least one polyol as described above. Thesilane-terminated monomeric diisocyanate comprises a monomericdiisocyanate fully reacted with an aminosilane or mercaptosilaneendcapper as described above. The optional multifunctional componentcomprises at least one of a polyether trisilane component, a polyethertetrasilane component, or a low molecular weight silane adductcomprising at least one of a trisilane adduct or a tetrasilane adduct,as described above.

In certain embodiments, the silane-terminated polyurethane prepolymercomponent comprises a prepolymer reaction product of at least onediisocyanate and at least one polyol with a mole ratio of isocyanategroups to hydroxy groups of about 0.5:1 to about 0.9:1, wherein theprepolymer reaction product is further reacted with a monomericdiisocyanate, followed by termination with an aminosilane endcapper ofthe formula: R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or a mercaptosilaneendcapper of the formula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x), wherein Rrepresents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

In certain other embodiments, the prepolymer component and monomericcomponent comprise a mixture of a silane-terminated polyurethaneprepolymer and a silane-terminated monomeric diisocyanate, with themixture comprising a reaction product of at least one diisocyanate andat least one polyol with a mole ratio of isocyanate groups to hydroxygroups of greater than about 2:1, wherein the reaction product isterminated with an aminosilane endcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x), or a mercaptosilane endcapper of theformula: HS—A¹—Si(R¹)_(x)(OR²)_(3-x), wherein R represents a C₁ to C₁₀alkyl group, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or agroup having the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ toC₁₀ linear, branched or cyclic alkylene group; R¹ represents a CH₃ orC₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ toC₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

Polyurethane prepolymers are prepared by the reaction of a diisocyanatewith a polyol. In some embodiments, a diisocyanate is reacted with apolyol at a temperature of about 60° C. or greater. In otherembodiments, a diisocyanate is reacted with a polyol at a temperature ofabout 70° C. or greater. In yet other embodiments, a diisocyanate isreacted with a polyol at a temperature of about 80° C. or greater. Incertain embodiments, the reaction time may be about 2 hours or greater.In other embodiments, the reaction time may be about 4 hours or greater.In yet other embodiments, the reaction time may be about 5 hours orgreater.

The reaction of a diisocyanate with a polyol may be enhanced with theuse of a catalyst. Suitable catalysts may include, but are not limitedto, dialkyltin dicarboxylates such as dibutyltin dilaurate (DBTDL) anddibutyltin diacetate, tertiary amines, the stannous salts of carboxylicacids such as stannous octoate and stannous acetate, and combinationsthereof. In certain embodiments, dibutyltin dilaurate is used as thecatalyst for the reaction of a diisocyanate and a polyol.

In the preparation of a silane-terminated polyurethane prepolymer, thesilane-containing compound used for the endcapping reaction may bechosen based on the mole ratio of isocyanate groups to hydroxy groups inthe reaction mixture. For example, if the mole ratio of isocyanategroups to hydroxy groups is greater than about 1.0/1, an aminosilane ora mercaptosilane may be used for the endcapping reaction. If the moleratio of isocyanate groups to hydroxy groups is less than about 1.0/1,an isocyanatosilane may be used for the endcapping reaction. In certainembodiments, the silane-containing compound is added slowly to apolyurethane prepolymer after reaction of the diisocyanate and polyol iscomplete. In some embodiments, the silane-containing compound is addedslowly for about 30 minutes or more. In other embodiments, thesilane-containing compound is added slowly for about 1 hour or more. Thetemperature may be kept unchanged during the addition of thesilane-containing compound. The extent of completion of reaction may bemonitored by Fourier Transform Infrared (FTIR) Spectroscopy through thedisappearance of the isocyanate peak in the FTIR spectrum.

In certain embodiments, a mixture of a silane-terminated polyurethaneprepolymer and a silane-terminated monomeric diisocyanate may beprepared through the aminosilane or mercaptosilane endcapping of areaction product of a diisocyanate and a polyol with a mole ratio ofisocyanate groups to hydroxy groups of greater than about 2:1. In otherembodiments, a reaction product of at least one diisocyanate and atleast one polyol with a mole ratio of isocyanate groups to hydroxygroups of less than about 2:1 is blended with additional monomericdiisocyanate to increase the mole ratio of isocyanate groups to hydroxygroups in the blend to greater than about 2:1. This mole ratio ofgreater than about 2:1 results in a polyurethane prepolymer reactionproduct that still contains free diisocyanate monomer. Endcapping withan aminosilane or a mercaptosilane results in the simultaneouspreparation of a silane-terminated polyurethane prepolymer and asilane-terminated monomeric diisocyanate.

In some embodiments, prepolymer molecular weights may be increased bythe use of a multi-step procedure comprising preparation of a prepolymerat a low mole ratio of isocyanate groups to hydroxy groups followed byblending of the formed prepolymer with additional monomeric diisocyanateto increase the mole ratio of isocyanate groups to hydroxy groups, withsubsequent endcapping with an aminosilane or mercaptosilane. In certainembodiments, the mole ratio of isocyanate groups to hydroxy groups isless than about 2:1 before blending with additional monomericdiisocyanate and endcapping with an aminosilane or mercaptosilane.

The above reaction products may be applied to a substrate, such as thesurface of concrete, asphalt, stone, rubber, plastic, metal, or wood bytechniques known in the art, prior to the cure of the composition. Incertain embodiments, the substrate may comprise composite materials, andin some embodiments the substrate may be in the form of a mat made fromrecycled rubber granules. Application techniques may include, but arenot limited to, spraying, brushing, rolling, squeegeeing, scraping,troweling, and combinations thereof.

Improved performance is typically obtained for firm, clean, and dry loadbearing substrate surfaces free of loose and brittle particles, andwithout substances which impair adhesion such as oil, grease, rubberskid marks, paint, or other contaminants. Surface preparation beforeapplication of the polyurethane composition as a coating, sealant,adhesive, or sports track binder can include water-blasting,sandblasting, cleaning, and drying, and the like.

A sports track binder is a representative high performance applicationwith requirements that are met by the described silane-terminatedpolyurethane compositions and reaction products. Sports track bindersare elastic materials that satisfy technical and environmentalrequirements for indoor and outdoor sports surfaces. These sportssurfaces are designed for multipurpose use and offer high wearresistance as well as specific sports-related properties such as spikeresistance. Sports track binders are used in sports halls, playgrounds,indoor arenas, and outdoor stadiums. Indoor sports halls includefacilities for track, gymnastics, school sports, and multipurpose use.Outdoor applications include athletic tracks, tennis courts, and stadiumwarning tracks.

Requirements for sports track binders include strength and elasticity asindicated by high tensile strength and high elongation values. Thedescribed silane-terminated polyurethane compositions and reactionproducts exhibit high tensile strength and high elongation values andare suitable for use as sports track binders, coatings, adhesives, andsealants.

A sports track binder may comprise a single layer material. Thedescribed silane-terminated polyurethane compositions are suitable foruse as single layer materials. A sports track binder may also comprisemultiple layers, which may include a primer, a base mat, a pore sealer,a coating layer, a sealing layer, and line-painting. The describedsilane-terminated polyurethane compositions are suitable for use as anyof these layers.

A coating layer may be applied in two or more coats. When applied to asubstrate, in certain embodiments, a silane-terminated polyurethanecomposition is provided for a coating layer that is at least about 0.5mm thick. In some embodiments, the silane-terminated polyurethanecomposition is about 0.5 mm to about 2 mm thick.

In certain embodiments, the bottom layer of a multiple layerconstruction utilizing the described polyurethane compositions comprisesa rubber material. In some embodiments, a bottom layer comprising aprefabricated or cast in place mat has a thickness of about 1 cm, acoating layer applied in two coats has a thickness of about 0.5 mm toabout 2 mm, and a sealing layer composition prepared using aliphaticdiisocyanates has a thickness of up to about 100 mils.

The following specific examples are given to illustrate the preparationof silane-terminated polyurethane compositions and silane-terminatedreaction products as discussed above.

EXAMPLES

Screening Formulation silylated prepolymer(s) 79.05 g  calcium carbonatefiller 3.00 g fumed silica filler 0.70 g solvent 17.17 g  DBTDL catalyst0.46 g Total 100.38 g 

Tensile Properties

Drawdowns of screening formulations were prepared with wet filmthicknesses of 20 mils (about 0.5 mm) and cured for 7 days at standardconditions. Dumbbell specimens were cut from the cured films with a DieC and tested according to specification ASTM D 412 Test Method A (rateof elongation: 20 in./min, about 500 mm/min) on an INSTRON 5566Universal Material Test System (Instron Corporation, Canton, Mass.).

General Procedure for Examples 1 and 2

A polyol and Mondur ML diisocyanate (mixture of 4,4′-diphenylmethanediisocyanate (MDI) and 2,4′-diphenylmethane diisocyanate) were blendedin various NCO/OH ratios according to the following tables. DBTDLcatalyst (0.02 parts) was added. The mixture was stirred with apropeller blade at 75 rpm and heated to 70° C. for 2-3 hours until thepercent NCO reached the theoretical value. Then, the endcapper3-ethylamino-2-methylpropyltrimethoxysilane (Silquest A-Link 15 from OSiSpecialties) was added slowly through an addition funnel, while thetemperature was kept at 70° C. Five to ten minutes after the end of theaddition, the mixture was checked by FTIR for complete conversion andconsequent disappearance of the NCO groups. Results are shown in Table 1and Table 2.

Example 1

TABLE 1 Prepolymer 1 2 3 4 5 Polyol Voranol Voranol Voranol VoranolVoranol 220-028 220-028 220-028 220-028 220-028 Molecular Weight 40004000 4000 4000 4000 NCO/OH ratio 1.6 2.0 2.4 2.8 3.2 Weight % Voranol220-028 85.70 80.89 76.59 72.72 69.22 Weight % Mondur ML 8.57 10.1111.49 12.73 13.85 Weight % DBTDL 0.02 0.02 0.02 0.02 0.02 Weight %A-Link 15 5.71 8.98 11.90 14.53 16.91 Prepolymer Viscosity At 56,80045,000 39,200 38,400 34,000 Ambient Temperature [mPas] MechanicalProperties Of The Screening Formulation Tensile Strength [MPa] 1.0 1.71.8 3.5 4.3 Elongation [%] 227 165 121 154 107

Example 2

TABLE 2 Prepolymer 6 4 7 8 Polyol Voranol Voranol Acclaim Acclaim220-056N 220-028 8200 12200 Molecular Weight 2000 4000 8000 12000 NCO/OHratio 2.0 2.8 4.4 6.0 Weight % Polyol 67.92 72.72 75.39 76.32 Weight %Mondur ML 16.98 12.73 10.37 9.54 Weight % DBTDL 0.02 0.02 0.02 0.02Weight % A-Link 15 15.08 14.53 14.23 14.12 Prepolymer Viscosity 121,60038,400 62,400 67,200 At Ambient Temperature [mPas] Mechanical PropertiesOf The Screening Formulation Tensile Strength 2.9 3.5 5.0 4.3 [MPa]Elongation [%] 80 154 176 222

Example 3 Prepolymer 9

Corresponding to a first NCO/OH ratio of 1.50, 71.83 parts of Acclaim8200 and 3.37 parts of Mondur ML diisocyanate were blended. DBTDLcatalyst (0.02 parts) was added. The mixture was stirred with apropeller blade at 75 rpm and heated to 70° C. for two hours until thepercent NCO reached the theoretical value of 0.50 percent. An additionalamount of 8.21 parts of Mondur ML diisocyanate was added to attain asecond NCO/OH ratio of 5.16. Then, 16.57 parts of the aminosilaneendcapper Silquest A-Link 15 were added slowly through an additionfunnel, while the temperature was kept at 70° C. Ten minutes after theend of the addition, the reaction was complete as confirmed by FTIR.

Properties:

-   Rheometer viscosity at 26° C.: 550,000 mPas-   Tensile strength: 5.8 MPa-   Elongation: 341%

Example 4 Prepolymer 10

Corresponding to a first NCO/OH ratio of 1.25, 69.82 parts of Acclaim4200 and 5.45 parts of Mondur ML diisocyanate were blended. DBTDLcatalyst (0.02 parts) was added. The mixture was stirred with apropeller blade at 75 rpm and heated to 70° C. for two hours until thepercent NCO reached the theoretical value of 0.49 percent. An additionalamount of 8.20 parts of Mondur ML diisocyanate was added to attain asecond NCO/OH ratio of 3.13. Then, 16.50 parts of aminosilane endcapperSilquest A-Link 15 were added slowly through an addition funnel, whilethe temperature was kept at 70° C. Ten minutes after the end of theaddition, the reaction was complete as confirmed by FTIR.

Properties:

-   Rheometer viscosity at 26° C.: 1,100,000 mPas-   Tensile strength: 8.2 MPa-   Elongation: 376%

Example 5 Formulation with Trisilane 1 (Polyether Trisilane)

Acclaim 6300 polyol (511.50 g), Silquest A-Link 35 isocyanatosilane(55.05 g), and DBTDL catalyst (0.611 g) were combined. The mixture wasstirred with a propeller blade at 75 rpm and heated to 70° C. Thepercent NCO decrease to zero was monitored by FTIR. The reaction wascomplete after 1 hour.

Tensile Properties Of Blends With Prepolymer 9: Weight percent Trisilane1 0% 5% 10% 15% 20% Tensile Strength [MPa] 5.8 8.8 9.5 9.0 8.0Elongation [%] 341 297 274 230 194

Tensile Properties Of Blends With Prepolymer 10 Weight percent Trisilane1 0% 10% 20% 30% Tensile Strength [MPa] 8.2 11.3 7.8 7.5 Elongation [%]376 295 185 172

Example 6 Formulation with Trisilane 2 (Low Molecular Weight Trisilane)

Aminosilane Silquest A-1170 bis-(gamma-trimethoxysilylpropyl)amine (56.2g) was combined with Silquest A-187gamma-glycidoxypropyltrimethoxysilane (38.9 g) and the mixture washeated in an oil bath at a temperature of 70° C. The reaction wasmonitored by GC/MS and proceeded very slowly. The mixture was heated to85° C. for three more days while the heat was switched off overnight.After four days the conversion was 98+ percent complete. Yield: 93 g ofa yellow liquid.

Tensile Properties Of Blends With Prepolymer 9: Weight percent Trisilane2 0% 2.5% 5% 10% Tensile Strength [MPa] 5.8 8.4 10.1 9.8 Elongation [%]341 287 297 249

Tensile Properties Of Blends With Prepolymer 10: Weight percentTrisilane 2 0% 2.5% 5% 10% Tensile Strength [MPa] 8.2 11.7 12.8 12.3Elongation [%] 376 348 333 289

Example 7 Formulation with Trisilane 3 (Low Molecular Weight Trisilane)

Silquest A-Link 35 isocyanatosilane (23.8 g) was added to aminosilaneSilquest A-1170 (40.8 g) in several small portions. The reaction wasexothermic and the flask was cooled in a water bath. After completeaddition the mixture was heated to 50° C. and the progress of thereaction was monitored by GC/MS until there was only a trace of A-Link35 left. Yield: 63 g of a yellow liquid.

Tensile Properties Of Blends With Prepolymer 10 Weight percent Trisilane3 0% 5% Tensile Strength [MPa] 5.8 9.3 Elongation [%] 341 303

As shown in FIGS. 1 and 2, synthesis of isocyanate terminatedpolyurethane prepolymers from disocyanate and polyol, exemplified by butnot limited to a polyol having a molecular weight of about 8000, havinga ratio of isocyanate groups to hydroxy groups (NCO/OH) less than 2:1,followed by blending with additional monomeric disocyanates to increasethe NCO/OH ratio to above 2:1 and a silane endcapper such as anaminosilane, results in a reaction product having a tensile strengthabove 580 psi, that is, above 4 MPa, and percentage of elongation above200%

As shown in FIGS. 3 and 4, synthesis of isocyanate terminatedpolyurethane prepolymers from disocyanate and polyol, exemplified by butnot limited to a polyol having a molecular weight of about 8000,followed by blending with additional monomeric disocyanates, a silaneendcapper, and a polyether trisilane or a low molecular weighttrisilane, results in a reaction product having high tensile strengthand high percentage of elongation.

The results shown in the above Tables and Figs. demonstrate high tensilestrengths and high elongation values suitable for high performanceapplications such as coatings, sealants, adhesives, and compositions.Higher NCO/OH ratios result in higher tensile strengths. Increasedmolecular weight of the polyol component leads to improved elongation.Performance is improved further through the use of multifunctionaltrisilanes. Other benefits of the prepared materials include the absenceof free isocyanates, the absence of bubbling during cure, improvedadhesion, and better UV resistance and weatherability than unmodifiedpolyurethanes.

In one embodiment a silane-terminated polyurethane composition maycomprise the reaction product of:

-   -   a) a silane-terminated polyurethane prepolymer component;    -   b) a silane-terminated monomeric diisocyanate component; and    -   c) optionally a trisilane or tetrasilane component:

Preferably, wherein:

-   -   a) the silane-terminated polyurethane prepolymer component        comprises at least one of:        -   i) a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 1.1:1 to about            2:1, said prepolymer reaction product terminated with an            aminosilane endcapper of the formula:            R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   or a mercaptosilane endcapper of the formula:            HS—A¹—Si(R¹)_(x)(OR²)_(3-x)        -   wherein R represents a C₁ to C₁₀ alkyl group, a group having            the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the            formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀            linear, branched or cyclic alkylene group; R¹ represents a            CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³            represents a C₁ to C₁₃ alkyl group; R⁴ represents a C₁ to            C₁₃ alkyl group; and x is 0 or 1; or        -   ii) a prepolymer reaction product of at least one            diisocyanate and at least one polyol with a mole ratio of            isocyanate groups to hydroxy groups of about 0.5:1 to about            0.9:1, said prepolymer reaction product terminated with an            isocyanatosilane endcapper of the formula:            OCN—A²—Si(R¹)_(x)(OR²)_(3-x)        -   wherein A² represents a C₁ to C₆ linear or branched alkylene            group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁            to C₄ alkyl group; and x is 0 or 1;    -   b) the silane-terminated monomeric diisocyanate component        comprises at least one monomeric diisocyanate fully reacted with        an aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1; and    -   c) the optional trisilane or tetrasilane component comprises at        least one of a polyether trisilane component, a polyether        tetrasilane component, or a low molecular weight silane adduct        comprising at least one of a trisilane adduct or a tetrasilane        adduct.

In certain embodiments of the silane-terminated polyurethanecomposition:

A) the polyether trisilane component may comprise at least one of:

-   -   a) the reaction product of at least one polyether triol        terminated with an isocyanatosilane endcapper of the formula:        OCN—A²—Si(R¹)_(x)(OR²)_(3-x)    -   wherein A² represents a C₁ to C₆ linear or branched alkylene        group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁ to        C₄ alkyl group; and x is 0 or 1; or    -   b) the multifunctional reaction product of at least one        polyether triol terminated with at least one diisocyanate with a        mole ratio of isocyanate groups to hydroxy groups of about 1.5:1        to about 2:1, said multifunctional reaction product terminated        with an aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1;

B) the polyether tetrasilane component may comprise at least one of:

-   -   a) the reaction product of at least one polyether tetraol        terminated with an isocyanatosilane endcapper of the formula:        OCN—A²—Si(R¹)_(x)(OR²)_(3-x)    -   wherein A² represents a C₁ to C₆ linear or branched alkylene        group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁ to        C₄ alkyl group; and x is 0 or 1; or    -   b) the multifunctional reaction product of at least one        polyether tetraol terminated with at least one diisocyanate with        a mole ratio of isocyanate groups to hydroxy groups of about        1.5:1 to about 2:1, said multifunctional reaction product        terminated with an aminosilane endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)    -   wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1; and,

C) the low molecular weight silane adduct may comprise the reactionproduct of at least one of:

-   -   a) i) at least one of HS—A¹—Si(R¹)_(x)(OR²)_(3-x), or        R⁷—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) and        -   ii) at least one of:

-   -   b) R⁵—(—OH)_(y) and OC—A²-Si(R¹)_(x)(OR²)_(3-x):        -   c) i) at least one of:        -   R⁵—(—NHR⁷)_(y), or        -   [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and        -   ii) at least one of:

-   -   d) i) [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and        -   ii) a diisocyanate;    -   e) i) a polyether triamine and ii) at least one of:

-   -   f) at least one of:        -   i) diethylenetriamine or triethylenetetramine, and ii) at            least one of:

-   -   -   wherein A² represents a C₁ to C₆ linear, or branched            alkylene group; A³ represents a C₁ to C₁₀ linear, branched            or cyclic alkylene group optionally interrupted with one or            more ether oxygen atoms; R⁵ represents a branched aliphatic            hydrocarbon residue, a branched aliphatic ether residue, or            an alkyl-substituted isocyanurate residue; R⁶ represents H            or a CH₃ group; R⁷ represents H, a C₁ to C₁₀ alkyl group, a            group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a            group having the formula —CH(COOR³)—CH₂(COOR⁴); A¹            represents a C₁ to C₁₀ linear, branched or cyclic alkylene            group; R¹ represents a CH₃ or C₂H₅ group; R² represents a C₁            to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴            represents a C₁ to C₁₃ alkyl group; x is 0 or 1; and y is 3            or 4.

In certain embodiments of the silane-terminated polyurethanecomposition, the at least one polyol may be selected from the groupconsisting of polyether polyols, polyester polyols, and combinationsthereof; or from the group consisting of polypropylene glycols,polytetramethylene glycols, polyoxyalkylene diols and triols,polycaprolactone diols and triols, and combinations thereof; preferablywherein the at least one polyol has a number average molecular weight inthe range of about 500 to about 20000.

In specific embodiments of the silane-terminated polyurethanecomposition, the at least one polyol may be selected from the groupconsisting of polyethylene glycols, polypropylene glycols,polytetramethylene glycols, polyethers prepared by the copolymerizationof cyclic ethers selected from the group consisting of ethylene oxide,propylene oxide, trimethylene oxide, tetrahydrofuran, and mixtures ofthese cyclic ethers, with aliphatic polyols selected from the groupconsisting of ethylene glycol, 1,3-butanediol, diethylene glycol,dipropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butylene glycol, and mixtures of these polyols, and combinationsselected from this group of glycols and polyethers; preferably whereinthe at least one polyol has a number average molecular weight in therange of about 500 to about 20000.

In certain embodiments of the silane-terminated polyurethanecomposition, each diisocyanate may be selected from the group consistingof hexamethylene diisocyanate (HDI), 4,4′-diphenylmethane diisocyanate(MDI), 2,4′-diphenylmethane diisocyanate, blends of 4,4′-diphenylmethanediisocyanate (MDI) with 2,4′-diphenylmethane diisocyanate, 2,4-toluenediisocyanate (TDI), 2,6-toluene diisocyanate, blends of 2,4-toluenediisocyanate (TDI) with 2,6-toluene diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof.

In certain embodiments of the silane-terminated polyurethanecomposition, the aminosilane, if present, may be selected from the groupconsisting of secondary aminosilanes having two methoxy groups,secondary aminosilanes having three methoxy groups, secondaryaminosilanes having two ethoxy groups, secondary aminosilanes havingthree ethoxy groups, and combinations thereof; wherein themercaptosilane, if present, comprises(3-mercaptopropyl)trimethoxysilane; and, wherein the isocyanatosilane,if present, is selected from the group consisting of isocyanatosilaneshaving two methoxy groups, isocyanatosilanes having three methoxygroups, isocyanatosilanes having two ethoxy groups, isocyanatosilaneshaving three ethoxy groups, and combinations thereof.

In certain embodiments of the silane-terminated polyurethanecomposition, the reaction product additionally comprises at least onecomponent selected from the group consisting of UV absorbers,antioxidants, stabilizers, mildewcides, biocides, fungicides, fire andflame retardants, fillers, pigments, plasticizers, solvents, catalysts,adhesion promoters, flow and leveling additives, wetting agents,antifoaming agents, rheology modifiers, and mixtures thereof.

In certain embodiments, the silane-terminated polyurethane compositionmay comprise a multicomponent formulation of a) the silane-terminatedpolyurethane prepolymer component; b) the silane-terminated monomericdiisocyanate component; and c) optionally the trisilane or tetrasilanecomponent, each as described in any of the above embodiments, whereinwhen components a, b, and optionally c are combined, a silane-terminatedpolyurethane reaction product is formed that has a tensile strength ofabout 4 MPa or greater and an elongation of about 200% or greater.

A method for making the silane-terminated polyurethane compositioncomprises:

-   -   a) providing a prepolymer component, a monomeric component, and        optionally at least one multifunctional component, wherein the        prepolymer component comprises a silane-terminated polyurethane        prepolymer, the monomeric component comprises a        silane-terminated monomeric diisocyanate, and the optional        multifunctional component comprises at least one of a trisilane        or tetrasilane component; each according to any of the above        embodiments, and    -   b) combining the prepolymer component, monomeric component, and        optionally at least one multifunctional component to form a        silane-terminated polyurethane reaction product wherein the        reaction product has a tensile strength of about 4 MPa or        greater and an elongation of about 200% or greater.

The method may further comprise applying the reaction product to asubstrate, preferably wherein said applying is selected from the groupconsisting of spraying, brushing, rolling, squeegeeing, scraping,troweling, and combinations thereof, and preferably wherein thesubstrate is selected from the group consisting of concrete, asphalt,stone, rubber, plastic, metal, and wood.

In the method wherein the prepolymer component comprises asilane-terminated polyurethane prepolymer component comprising aprepolymer reaction product of at least one diisocyanate and at leastone polyol with a mole ratio of isocyanate groups to hydroxy groups ofabout 0.5:1 to about 0.9:1, said prepolymer reaction product may befurther reacted with a monomeric diisocyanate, followed by terminationwith an aminosilane endcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)or a mercaptosilane endcapper of the formula:HS—A¹—Si(R¹)_(x)(OR²)_(3-x)wherein R represents a C₁ to C₁₀ alkyl group, a group having the formula—A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula—CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear, branched orcyclic alkylene group; R¹ represents a CH₃ or C₂H₅ group; R² representsa C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃ alkyl group; R⁴represents a C₁ to C₁₃ alkyl group; and x is 0 or 1.

In the method wherein the prepolymer component and monomeric componentcomprise a mixture of a silane-terminated polyurethane prepolymer and asilane-terminated monomeric diisocyanate, said mixture comprising atleast one of:

-   -   a) a reaction product of at least one diisocyanate and at least        one polyol with a mole ratio of isocyanate groups to hydroxy        groups of greater than about 2:1, or    -   b) a reaction product of at least one diisocyanate and at least        one polyol with a mole ratio of isocyanate groups to hydroxy        groups of less than about 2:1 blended with additional monomeric        diisocyanate to increase the mole ratio of isocyanate groups to        hydroxy groups in the blend to greater than about 2:1;        said reaction product is terminated with an aminosilane        endcapper of the formula:        R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x)        or a mercaptosilane endcapper of the formula:        HS—A¹—Si(R¹)_(x)(OR²)_(3-x)        wherein R represents a C₁ to C₁₀ alkyl group, a group having the        formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a group having the formula        —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀ linear,        branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅        group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁        to C₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x        is 0 or 1.

In one embodiment of the method wherein the prepolymer componentcomprises a silane-terminated polyurethane prepolymer componentcomprising a prepolymer reaction product of at least one diisocyanateand at least one polyol with a mole ratio of isocyanate groups tohydroxy groups of about 0.5:1 to about 0.9:1, said prepolymer reactionproduct is terminated with an isocyanatosilane endcapper of the formula:OCN—A²—Si(R¹)_(x)(OR²)_(3-x)wherein A² represents a C₁ to C₆ linear or branched alkylene group; R¹represents a CH₃ or C₂H₅ group; R² represents a C₁ to C₄ alkyl group;and x is 0 or 1; and the prepolymer component is blended for reactionwith the silane-terminated monomeric diisocyanate component whichcomprises at least one monomeric diisocyanate fully reacted with anaminosilane endcapper or a mercaptosilane endcapper

Although the invention has been described in detail through the abovedetailed description and the preceding examples, these examples are forthe purpose of illustration only and it is understood that variationsand modifications can be made by one skilled in the art withoutdeparting from the spirit and the scope of the invention. It should beunderstood that the embodiments described above are not only in thealternative, but can be combined.

1. A silane-terminated polyurethane composition comprising the reactionproduct of: a) a silane-terminated polyurethane prepolymer componentcomprising at least one of: a prepolymer reaction product of at leastone diisocyanate and at least one polyol with a mole ratio of isocyanategroups to hydroxy groups of about 1.1:1 to about 2:1, said prepolymerreaction product terminated with an aminosilane endcapper of theformula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1; b)a silane-terminated monomeric diisocyanate component comprising at leastone monomeric diisocyanate fully reacted with an aminosilane endcapperof the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1; andc) optionally a trisilane or tetrasilane component comprising at leastone of a polyether trisilane component, a polyether tetrasilanecomponent, or a silane adduct comprising at least one of a trisilaneadduct or a tetrasilane adduct; wherein the reaction product has atensile strength of about 4 MPa or greater and an elongation of about200% or greater.
 2. The silane-terminated polyurethane composition ofclaim 1, wherein the polyether trisilane component comprises at leastone of: a) the reaction product of at least one polyether triolterminated with an isocyanatosilane endcapper of the formula:OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A² represents a C₁ to C₆ linear orbranched alkylene group; R¹ represents a CH₃ or C₂H₅ group; R²represents a C₁ to C₄ alkyl group; and x is 0 or 1; or b) themultifunctional reaction product of at least one polyether triolterminated with at least one diisocyanate with a mole ratio ofisocyanate groups to hydroxy groups of about 1.5:1 to about 2:1, saidmultifunctional reaction product terminated with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) or a mercaptosilane endcapper of theformula:HS—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or
 1. 3.The silane-terminated polyurethane composition of claim 1, wherein thepolyether tetrasilane component comprises at least one of: a) thereaction product of at least one polyether tetraol terminated with anisocyanatosilane endcapper of the formula:OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A² represents a C₁ to C₆ linear orbranched alkylene group; R¹ represents a CH₃ or C₂H₅ group; R²represents a C₁ to C₄ alkyl group; and x is 0 or 1; or b) themultifunctional reaction product of at least one polyether tetraolterminated with at least one diisocyanate with a mole ratio ofisocyanate groups to hydroxy groups of about 1.5:1 to about 2:1, saidmultifunctional reaction product terminated with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) or a mercaptosilane endcapper of theformula:HS—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or
 1. 4.The silane-terminated polyurethane composition of claim 1, wherein thesilane adduct comprises the reaction product of at least one of: a) i)at least one of HS—A¹—Si(R¹)_(x)(OR²)_(3-x), orR⁷—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) and ii) at least one of:

b) R⁵—(—OH)_(y) and OCN—A²—Si(R¹)_(x)(OR²)_(3-x); c) i) at least one of:R⁵—(—NHR⁷)_(y), or [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and ii) at least oneof:

d) [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH and ii) a diisocyanate; e) i) apolyether triamine and ii) at least one of:

f) at least one of: i) diethylenetriamine or triethylenetetramine, andii) at least one of:

wherein A² represents a C₁ to C₆ linear, or branched alkylene group; A³represents a C₁ to C₁₀ linear, branched or cyclic alkylene groupoptionally interrupted with one or more ether oxygen atoms; R⁵represents a branched aliphatic hydrocarbon residue, a branchedaliphatic ether residue, or an alkyl-substituted isocyanurate residue;R⁶ represents H or a CH₃ group; R⁷ represents H, a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; x is 0 or 1; and yis 3 or
 4. 5. The silane-terminated polyurethane composition of claim 1,wherein the at least one polyol is selected from the group consisting ofpolyether polyols, polyester polyols, and combinations thereof.
 6. Thesilane-terminated polyurethane composition of claim 1, wherein the atleast one polyol is selected from the group consisting of polypropyleneglycols, polytetramethylene glycols, polyoxyalkylene diols and triols,polycaprolactone diols and triols, and combinations thereof.
 7. Thesilane-terminated polyurethane composition of claim 1, wherein the atleast one polyol is selected from the group consisting of polyethyleneglycols, polypropylene glycols, polytetramethylene glycols, polyethersprepared by the copolymerization of cyclic ethers selected from thegroup consisting of ethylene oxide, propylene oxide, trimethylene oxide,tetrahydrofuran, and mixtures of these cyclic ethers, with aliphaticpolyols selected from the group consisting of ethylene glycol,1,3-butanediol, diethylene glycol, dipropylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,4-butylene glycol, and mixtures of thesepolyols, and combinations selected from this group of glycols andpolyethers.
 8. The silane-terminated polyurethane composition of claim1, wherein each diisocyanate is selected from the group consisting ofhexamethylene diisocyanate (HDI), 4,4′-diphenylmethane diisocyanate(MDI), 2,4′-diphenylmethane diisocyanate, blends of 4,4′-diphenylmethanediisocyanate (MDI) with 2,4′-diphenylmethane diisocyanate, 2,4-toluenediisocyanate (TDI), 2,6-toluene diisocyanate, blends of 2,4-toluenediisocyanate (TDI) with 2,6-toluene diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof.
 9. Thesilane-terminated polyurethane composition of claim 1, wherein eachdiisocyanate comprises a blend of 4,4′-diphenylmethane diisocyanate(MDI) with 2,4′-diphenylmethane diisocyanate.
 10. The silane-terminatedpolyurethane composition of claim 1, wherein the aminosilane is selectedfrom the group consisting of secondary aminosilanes having two methoxygroups, secondary aminosilanes having three methoxy groups, secondaryaminosilanes having two ethoxy groups, secondary aminosilanes havingthree ethoxy groups, and combinations thereof.
 11. The silane-terminatedpolyurethane composition of claim 1, wherein the aminosilane is selectedfrom the group consisting of bis(trimethoxysilylpropyl)amine,3-ethylamino-2-methylpropyltrimethoxysilane,N-(n-butyl)-3-aminopropyltrimethoxysilane, and combinations thereof. 12.The silane-terminated polyurethane composition of claim 1, wherein theat least one polyol has a number average molecular weight in the rangeof about 500 to about
 20000. 13. The silane-terminated polyurethanecomposition of claim 1, wherein the at least one polyol comprises apolypropylene glycol with a number average molecular weight in the rangeof about 4000 to about 12000, and wherein said polypropylene glycol hasa degree of unsaturation of less than about 0.04 meq/g.
 14. Amulticomponent formulation comprising: a) at least one of asilane-terminated polyurethane prepolymer component comprising aprepolymer reaction product of at least one diisocyanate and at leastone polyol with a mole ratio of isocyanate groups to hydroxy groups ofabout 1.1:1 to about 2:1, said prepolymer reaction product terminatedwith an aminosilane endcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1; orb) at least one monomeric diisocyanate fully reacted with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹ 13 Si(R¹)_(x)(OR²)_(3-x), or agroup having the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ toC₁₀ linear, branched or cyclic alkylene group; R¹ represents a CH₃ orC₂H₅ group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ toC₁₃ alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1;and c) optionally at least one of a polyether trisilane component, apolyether tetrasilane component, or a silane adduct comprising at leastone of a trisilane adduct or a tetrasilane adduct; wherein whencomponents a, b, and optionally c are reacted, a silane-terminatedpolyurethane reaction product is formed that has a tensile strength ofabout 4 MPa or greater and an elongation of about 200% or greater. 15.The multicomponent formulation of claim 14, wherein the polyethertrisilane component comprises at least one of: a) the reaction productof at least one polyether triol terminated with an isocyanatosilaneendcapper of the formula:OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A² represents a C₁ to C₆ linear orbranched alkylene group; R¹ represents a CH₃ or C₂H₅ group; R²represents a C₁ to C₄ alkyl group; and x is 0 or 1; or b) themultifunctional reaction product of at least one polyether triolterminated with at least one diisocyanate with a mole ratio ofisocyanate groups to hydroxy groups of about 1.5:1 to about 2:1, saidmultifunctional reaction product terminated with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) or a mercaptosilane endcapper of theformula:HS—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or
 1. 16.The multicomponent formulation of claim 14, wherein the polyethertetrasilane component comprises at least one of: a) the reaction productof at least one polyether tetraol terminated with an isocyanatosilaneendcapper of the formula:OCN—A²—Si(R¹)_(x)(OR²)_(3-x) wherein A² represents a C₁ to C₆ linear orbranched alkylene group; R¹ represents a CH₃ or C₂H₅ group; R²represents a C₁ to C₄ alkyl group; and x is 0 or 1; or b) themultifunctional reaction product of at least one polyether tetraolterminated with at least one diisocyanate with a mole ratio ofisocyanate groups to hydroxy groups of about 1.5:1 to about 2:1, saidmultifunctional reaction product terminated with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) or a mercaptosilane endcapper of theformula:HS—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or
 1. 17.The multicomponent formulation of claim 14, wherein the silane adductcomprises the reaction product of at least one of: a) i) at least one ofHS—A¹—Si(R¹)_(x)(OR²)_(3-x), or R⁷—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) and ii)at least one of:

b) R⁵—(—OH)_(y) and OCN—A²—Si(R¹)_(x)(OR²)_(3-x); c) at least one of: i)R⁵—(NHR⁷)_(y), or [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH, and ii) at least oneof:

d) i) [(R²O)_(3-x)(R¹)_(x)Si—A¹—]₂NH and ii) a diisocyanate; e) i) apolyether triamine and ii) at least one of:

f) at least one of: i) diethylenetriamine or triethylenetetramine, andii) at least one of:

wherein A² represents a C₁ to C₆ linear, or branched alkylene group; A³represents a C₁ to C₁₀ linear, branched or cyclic alkylene groupoptionally interrupted with one or more ether oxygen atoms; R⁵represents a branched aliphatic hydrocarbon residue, a branchedaliphatic ether residue, or an alkyl-substituted isocyanurate residue;R⁶ represents H or a CH₃ group; R⁷ represents H, a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; x is 0 or 1; and yis 3 or
 4. 18. The multicomponent formulation of claim 14, wherein theat least one polyol is selected from the group consisting of polyetherpolyols, polyester polyols, and combinations thereof.
 19. Themulticomponent formulation of claim 14, wherein the at least one polyolis selected from the group consisting of polypropylene glycols,polytetramethylene glycols, polyoxyalkylene diols and triols,polycaprolactone diols and triols, and combinations thereof.
 20. Themulticomponent formulation of claim 14, wherein the at least one polyolis selected from the group consisting of polyethylene glycols,polypropylene glycols, polytetramethylene glycols, polyethers preparedby the copolymerization of cyclic ethers selected from the groupconsisting of ethylene oxide, propylene oxide, trimethylene oxide,tetrahydrofuran, and mixtures of these cyclic ethers, with aliphaticpolyols selected from the group consisting of ethylene glycol,1,3-butanediol, diethylene glycol, dipropylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,4-butylene glycol, and mixtures of thesepolyols, and combinations selected from this group of glycols andpolyethers.
 21. The multicomponent formulation of claim 14, wherein eachdiisocyanate is selected from the group consisting of hexamethylenediisocyanate (HDI), 4,4′-diphenylmethane diisocyanate (MDI),2,4′-diphenylmethane diisocyanate, blends of 4,4′-diphenylmethanediisocyanate (MDI) with 2,4′-diphenylmethane diisocyanate, 2,4-toluenediisocyanate (TDI), 2,6-toluene diisocyanate, blends of 2,4-toluenediisocyanate (TDI) with 2,6-toluene diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof.
 22. Themulticomponent formulation of claim 14, wherein each diisocyanatecomprises a blend of 4,4′-diphenylmethane diisocyanate (MDI) with2,4′-diphenylmethane diisocyanate.
 23. The multicomponent formulation ofclaim 14, wherein the aminosilane is selected from the group consistingof secondary aminosilanes having two methoxy groups, secondaryaminosilanes having three methoxy groups, secondary aminosilanes havingtwo ethoxy groups, secondary aminosilanes having three ethoxy groups,and combinations thereof.
 24. The multicomponent formulation of claim14, wherein the aminosilane is selected from the group consisting ofbis(trimethoxysilylpropyl)amine,3-ethylamino-2-methylpropyltrimethoxysilane,N-(n-butyl)-3-aminopropyltrimethoxysilane, and combinations thereof. 25.The multicomponent formulation of claim 14, wherein the at least onepolyol has a number average molecular weight in the range of about 500to about
 20000. 26. The multicomponent formulation of claim 14, whereinthe at least one polyol comprises a polypropylene glycol with a numberaverage molecular weight in the range of about 4000 to about 12000, andwherein said polypropylene glycol has a degree of unsaturation of lessthan about 0.04 meq/g.
 27. The multicomponent formulation of claim 14,wherein the reaction product has a tensile strength of about 10 MPa orgreater.
 28. The multicomponent formulation of claim 14, wherein thereaction product has an elongation of about 300% or greater.
 29. Amulticomponent formulation comprising: a) at least one of: asilane-terminated polyurethane prepolymer component comprising aprepolymer reaction product of at least one diisocyanate and at leastone polyol with a mole ratio of isocyanate groups to hydroxy groups ofabout 1.1:1 to about 2:1, said prepolymer reaction product terminatedwith an aminosilane endcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1; orb) at least one monomeric diisocyanate component selected from the groupconsisting of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethanediisocyanate, blends of 4,4′-diphenylmethane diisocyanate with2,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluenediisocyanate, blends of 2,4-toluene diisocyanate with 2,6-toluenediisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane,dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof, the atleast one monomeric diisocyanate fully reacted with an aminosilaneendcapper of the formula:R—NH—A¹—Si(R¹)_(x)(OR²)_(3-x) wherein R represents a C₁ to C₁₀ alkylgroup, a group having the formula —A¹—Si(R¹)_(x)(OR²)_(3-x), or a grouphaving the formula —CH(COOR³)—CH₂(COOR⁴); A¹ represents a C₁ to C ₁₀linear, branched or cyclic alkylene group; R¹ represents a CH₃ or C₂H₅group; R² represents a C₁ to C₄ alkyl group; R³ represents a C₁ to C₁₃alkyl group; R⁴ represents a C₁ to C₁₃ alkyl group; and x is 0 or 1; andc) optionally at least one of a polyether trisilane component, apolyether tetrasilane component, or a silane adduct component comprisingat least one of a trisilane adduct or a tetrasilane adduct; wherein whencomponents a, b, and optionally c are reacted, a silane-terminatedpolyurethane reaction product is formed that has a tensile strength ofabout 4 MPa or greater and an elongation of about 200% or greater. 30.The multicomponent formulation of claim 29, wherein the diisocyanate ofthe prepolymer reaction product component and the monomeric diisocyanatecomponent comprise a blend of 4,4′-diphenylmethane diisocyanate with2,4′-diphenylmethane diisocyanate.